Effect of particle structure and surface chemistry on PMMA adsorption to silica nanoparticles.

The interphase layer of polymers adsorbed to silica surfaces can be affected by the surface silanol density as well as the relative size of the polymer compared with the size of the adsorbing substrate. Here, the nonequilibrium adsorption of PMMA onto individual colloidal Stober silica (SiO(2)) particles, where R(particle) (100 nm) > R(PMMA) (approximately 6.5 nm) was compared with the adsorption onto fumed silica, where R(particle) (7 nm) approximately R(PMMA) (6.5 nm) < R(aggregate) (approximately 1000 nm), as a function of both silanol density [SiOH] and hydrophobility. In the former case, TEM images showed that the PMMA adsorbed onto individual nanoparticles, so that the number of PMMA chains/bead could be calculated, whereas in the latter case bridging of PMMA between aggregates occurred. The anchoring point densities were comparable to the silanol densities, suggesting that PMMA adsorbed as trains rather than loops. For hydrophilic SiO(2), T(g) increased with [SiOH], as more carbonyl groups hydrogen bonded to the silanols, and was independent of particle morphology. For methylated silica, (CH(3))(3)SiO(2), the adsorption isotherms were identical for colloidal and fumed silica, but T(g) was depressed for the former, and comparable to the bulk value for the latter. The increased T(g) of PMMA adsorbed onto fumed (CH(3))(3)SiO(2) was attributed to the larger loops formed by the bridging PMMA chains between the silica aggregates.